Multicrystalline silicon ingots, silicon masteralloy, method for increasing the yield of multicrystalline silicon ingots for solar cells

ABSTRACT

The present invention comprises directionally solidified multicrystalline silicon ingots, a silicon masteralloy for increasing the efficiency of solar cells made from wafers cut from the silicon ingots, method for increasing the yield when producing multicrystalline silicon ingots from a silicon melt by directional solidification. Further the present invention comprises a method for preparing said silicon masteralloy.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of copending U.S. application Ser.No. 14/916,406, filed Mar. 3, 2016, which is a 371 of PCT/N02014/050165filed on Sep. 9, 2014 which, in turn, claimed the priority of NorwegianPatent Application No. 20131216 filed on Sep. 9, 2013, InternationalPatent Application No. PCT/N02013/000046 filed on Oct. 1, 2013 andNorwegian Patent Application No. 20140621 filed on May 15, 2014, allapplications are incorporated herein by reference.

FIELD OF INVENTION

The present invention comprises a silicon composition for increasedyield of multicrystalline silicon ingots, and for increasing theefficiency of solar cells made from wafers cut from the silicon ingots.In addition the present invention comprises a method for increasing theyield when producing multicrystalline silicon ingots from a silicon meltby directional solidification. Further the present invention comprises asilicon masteralloy and method for preparing said silicon masteralloyfor addition to the silicon melt for producing the multicrystallinesilicon ingots in order to increase the yield of multicrystallinesilicon ingots for solar cells, and for increasing the efficiency ofsolar cells made from wafers cut from the silicon ingots.

BACKGROUND ART

By directional solidification of silicon for production ofmulticrystalline silicon ingots a so-called “red zone” is formed alongthe outer part of the ingot, in the lower end of the ingot and at thetop end of the ingot. The red zone is typically 2-3 cm thick and may becharacterized by a short life time for minority carriers. The life timeof minority carriers in the red zone area is measured to below thequality requirement of above 2 μs. The red zone area of directionallysolidified ingots is therefore normally cut away and thus not used forwafers for solar cell production. The red zone area of the directionalsolidified multicrystalline silicon ingot reduces the yield of theingot. The red zone appears both in polysilicon and in compensatedsilicon (silicon containing both boron and phosphorus) even though thered zone normally is thicker in compensated silicon than in polysilicon.

The reason of the formation of red zone at the lower end, along thewalls and at the upper end of the directional solidified silicon ingotshas been related to different kinds of defects; see Y. Boulfrad:Investigation of the Red Zone of multicrystalline Silicon Ingots forSolar cells; Doctoral Thesis at NTNU, Norway 2012:84. The main type ofdefect is caused by Fe and 0 diffusing into the solid silicon from thecrucible and/or from the coating used in the crucible. Further defectssuch as dislocations and a synergistic effect between the differenttypes of defects may also be present. Further there is a tendency thatparticles are present near the upper end of directional solidifiedsilicon ingots. The upper part of the ingots must also for this reasonbe cut off and thereby limiting the yield.

In order to increase the yield of the silicon ingots it is desirable tominimize or totally avoid formation of the red zone, particularly in thelower end of the silicon ingots which would increase the useful part ofthe silicon ingots suitable for wafers and solar cell processing. Itwould further be advantageous if the content of particles near the upperend of the directional solidified silicon ingot could be reduced.

SUMMARY OF THE INVENTION

The present invention is conceived to solve or at least alleviate theproblems identified above. Specifically, an object of the invention isto provide a silicon ingot and a method in which the yield whenproducing multicrystalline silicon ingots for solar cells from a siliconmelt is increased, by improving the electrical properties (minoritycarrier lifetime and solar cell efficiency) of the ingot both in the redzone and in the bulk of the ingot.

The present invention comprises directionally solidifiedmulticrystalline silicon ingots, wherein said ingot comprises elementalcalcium added to a silicon melt in an amount chosen from at least one ofthe following ranges: 5-9.99 ppmw, 10-500 ppmw, 500-550 ppmw. The yieldof the directionally solidified multicrystalline silicon ingot isincreased resulting in higher utilisation of the ingot when cut towafers, thus increasing the wafer yield. Further, a silicon compositionaccording to the present invention wherein elemental calcium is added tothe silicon melt in an amount chosen from at least one of the followingranges: 5-9.99, 10-500, 10-250, 20-250, 10-150, 20-150, 10-100, 10-150ppmw. The silicon melt is chosen among polysilicon and compensatedsilicon.

The present invention comprises a silicon masteralloy for addition tosilicon when making directionally solidified multicrystalline siliconingot to increase yield and electrical properties of the ingot, in whichsaid silicon masteralloy comprises elemental calcium in an amount chosenfrom at least one of the following ranges: 0.5-20 weight %, 1-15 weight%, 5-15 weight %, the remaining being high purity silicon.

Further the present invention comprises a silicon masteralloy forincreased yield in multicrystalline silicon ingots in which said siliconmasteralloy comprises elemental calcium in an amount chosen from atleast one of the following ranges: 0.5-20 weight %, 1-15 weight %, 5-15weight %, the remaining being high purity silicon. Furthermore, saidsilicon masteralloy is optionally added to a silicon melt whendirectionally solidifying silicon ingot.

Furthermore a method for increasing the yield of directional solidifiedmulticrystalline silicon ingots is also comprised in which elementalcalcium is added to the silicon melt in an amount chosen from at leastone of the following ranges: 5-9.99 ppmw, 10-500 ppmw, 500-550 ppmwprior to subjecting the silicon melt to directional solidification in acrucible. In the present invention calcium is added to the silicon meltin an amount chosen from at least one of the following ranges: 5-9.99,10-500, 10-250, 20-250, 10-150, 20-150, 10-100, 10-150, 500-550 ppmw.

The present invention comprises a method for preparing a siliconmasteralloy for increasing the yield of multicrystalline silicon ingots,in which said method comprises addition of elemental calcium to a moltensilicon in an amount chosen from at least one of the following ranges:0.5-20 weight %, 1-15 weight %, 5-15 weight %, homogenizing theresulting alloy and solidifying said alloy to provide said siliconmasteralloy. Said silicon masteralloy is optionally added to a siliconmelt when directionally solidifying a silicon ingot.

The silicon melt which also should be understood as molten silicon canbe chosen among at least one of the following: a high purity siliconmelt, compensated silicon and polysilicon. According to the inventionsaid silicon masteralloy described above is added to a charge comprisingsilicon for producing multicrystalline silicon ingots with increasedyield. In the present invention silicon ingots with increased yield areproduced by directionally solidifying multi-crystalline silicon ingotsfrom said silicon melt. The present invention also concerns use of amaster alloy comprising elemental calcium in an amount chosen from atleast one of the following ranges: 0.5-20 weight %, 1-15 weight %, 5-15weight %, the remaining being high purity silicon for directionallysolidifying multicrystalline silicone ingot for increasing yield andelectrical properties of said ingot.

The present invention thus relates to a method for minimizing orremoving the red zone in multicrystalline silicon ingots, whereinelemental calcium in an amount between 10 and 500 ppmw is added to thesilicon before the silicon is subjected to directional solidification ina crucible.

Further the present invention relates to a method for minimizing orremoving the red zone in directionally solidified multicrystallinesilicon ingots, in which elemental calcium is added to a silicon melt inan amount chosen from at least one of the following ranges: 5-9.99 ppmw,10-500 ppmw, 500-550 ppmw prior to subjecting the silicon to directionalsolidification in a crucible.

According to a preferred embodiment the elemental calcium are added tothe silicon in an amount of between 20 and 250 ppmw.

Elemental calcium can be added to the silicon in the crucible fordirectional solidification before the silicon is melted or after thesilicon is melted.

It has surprisingly been found that the addition of small amounts ofelemental calcium substantially reduces the extent of the red zone indirectionally solidified multicrystalline silicon ingots.

The effect of reducing the red zone by adding elemental calcium to thesilicon before directional solidification has been found to be effectiveboth for boron doped polysilicon and for so-called compensated highpurity silicon which contains both boron and phosphorus.

A shorter part of the lower end of the directionally solidified siliconingot can thus be cut away before wafering, thereby increasing the yieldof the ingots. The same is true for the upper end of the ingot and thesides of the ingots.

SHORT DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the efficiency of solar cells made fromwafers cut from the lower part of ingots A and B in Example 1 as afunction of mm from bottom of the ingots.

FIG. 2 is a diagram showing the efficiency of solar cells made fromwafers cut from the whole height of ingots A and B in Example 1 as afunction of mm from bottom of the ingots.

FIG. 3 is a diagram showing the efficiency of solar cells made fromwafers cut from the lower part of ingots C and D in Example 1 as afunction of mm from bottom of the ingots.

FIG. 4 is a diagram showing the efficiency of solar cells made fromwafers cut from the whole height of ingots C and D in Example 1 as afunction of mm from bottom of the ingots.

FIG. 5 is a diagram showing the efficiency of solar cells made fromwafers cut from the lower part of ingots E, F and G in Example 2 as afunction of mm from bottom of the ingots.

FIG. 6 is a diagram showing the efficiency of solar cells made fromwafers cut from the whole height of ingots E, F, and G in Example 2 as afunction of mm from bottom of the ingots.

FIG. 7 shows IR image of brick from a G5 ingot with addition ofsilicon-calcium masteralloy addition to the right and without additionof silicon-calcium masteralloy addition to the left.

FIG. 8 shows lifetime scans of one adjacent to center brick from allfour sides, a) for an ingot with 100% virgin polysilicon made withoutaddition of silicon-calcium masteralloy and average lifetime 4.0 μs, b)for an ingot with 100% ESS® with addition of silicon-calcium masteralloyand average lifetime 5.3 μs and c) for an ingot with 100% ESS® withaddition of silicon-calcium masteralloy (bottom) and average lifetime7.1 μs. Scale of the lifetime scan from 0.4 to 8 μs.

FIG. 9 shows efficiency of solar cells made from wafers cut fromadjacent to centre brick and corner brick from G5 ingot made withaddition of silicon-calcium masteralloy compared to reference ingots(adjacent to centre brick) of 100% virgin polysilicon and 100% ESS® madein the same furnace. All wafers were processed at International SolarEnergy Research Centre in Konstanz, Germany, (ISC).

DETAILED DESCRIPTION

“Calcium” within the context of the of the present invention, shall beunderstood as elemental calcium.

Regarding the present invention it has been observed that addition ofcalcium to the silicon charge when producing directional solidifiedmulticrystalline silicon ingots can significantly improve the ingotproperties, in particular the so-called red-zone (low lifetime regions)close to the crucible, thus increasing the yield of the ingot. Inaddition enhancement of the cell efficiencies of solar cells from thisregion has been observed according to the present invention.

As the melting temperature of calcium is much lower than the meltingtemperature of silicon, a challenge when adding elemental calcium to thesilicon charge is that calcium melts at a lower temperature thansilicon. This may cause reactions of molten calcium with the coating andthe crucible. These reactions may in some cases result in sticking ofthe ingot to the crucible, which may lead to cracking of the ingot. Inone embodiment of the present invention elemental calcium is added as asilicon-calcium masteralloy containing calcium in the range 0.5-20weight %. The silicon-calcium masteralloy can then be added to thesilicon charge when producing multicrystalline silicon ingot. Additionof calcium in the form of a silicon-calcium masteralloy according to thepresent invention will ensure melting of calcium close to the meltingtemperature of silicon. In one embodiment of the present invention,addition of a silicon-calcium masteralloy to a silicon melt forproducing multicrystalline silicon ingots, will ensure a simplifiedaddition of calcium and solve any problem that addition of elementalcalcium may cause.

Example 1

Four directionally solidified multicrystalline silicon ingots A, B, Cand D of 16 kg each are produced at the same time in a furnace with foursolidification chambers. This means that all four ingots A to D wereproduced under exactly the same conditions. Ingot A was a polysiliconingot which was doped with boron to obtain a resistivity of between 1and 1.3 ohm cm measured at the lower end of the ingot without additionof calcium. Ingot B was a polysilicon with addition of 40 ppmw elementalcalcium, according to the present invention. Ingot C was compensatedsilicon containing both boron and phosphorus produced by Elkem Solar AS,(ESS®), and having a resistivity of between 1 and 1.3 ohm cm measured atthe lower end of the ingot. Ingot D was compensated silicon produced byElkem Solar AS, (ESS®), with addition of 40 ppmw elemental calcium,according to the present invention.

The height of the Ingots A to D was 145 mm and the cross-sectional areawas 220 mm×220 mm.

5 mm was cut away from the lower end of the ingots A to D. As statedabove normally 3-5 cm are cut from ingots used for wafering. Normal cutswere made on the long sides of the ingots. The reduction of red zonecould thus only be demonstrated in the lower part of the ingots. Waferswere cut along the height of the four ingots A to D and processed tosolar cells using conventional processing methods and the efficiency ofthe solar cells were measured. The result for efficiency of solar cellsmade from ingots A and B are shown in FIGS. 1 and 2 and the results foringots C and D made from compensated silicon produced by Elkem Solar ASare shown in FIGS. 3 and 4.

FIG. 1 shows the efficiency of solar cells made from wafers cut from thelower part of ingots A and B. As shown in FIG. 1 the efficiency of solarcells made from wafers from ingot B (polysilicon to which was added 40ppmw elemental calcium), was much higher than for the solar cells madefrom wafers from the lower part of ingot A, which did not containelemental calcium.

It can further be seen from FIG. 1 that solar cells made from wafers cutonly about 5 mm from the bottom of Ingot B had an efficiency of almost16% while a solar cell made from a wafer cut about 10 mm from the bottomof ingot A showed an efficiency of below 15%.

Finally it can be seen from FIG. 1 that the solar cells made from thelower part of Ingot B reached about 17% efficiency for wafers cut 15 mmfrom the lower end of the ingot while the same efficiency for solarcells made from wafers from Ingot A first reaches 17% efficiency whencut about 25 mm from the lower end of ingot A.

FIG. 2 shows the efficiency of solars cells made from wafers cut alongthe whole height of Ingot A and Ingot B.

It can be seen from FIG. 2 that the solar cells made from wafers fromingot B have a high efficiency along the total height of the ingot.

FIG. 3 shows the efficiency of solar cells made from wafers cut from thelower parts of Ingots C and D. As shown in FIG. 3, solar cells made fromwafers cut from the lower end of ingot D (compensated silicon producedby Elkem AS with addition of 40 ppmw elemental calcium) shows a muchhigher efficiency then solar cells made from wafers from the lower endof Ingot C (compensated silicon produced by Elkem AS without calciumaddition).

FIG. 4 shows the efficiency of solar cells made from wafers cut alongthe whole height of Ingot C and Ingot D. It can be seen that the solarcells made from ingot D at an average have a higher efficiency then thesolar cells made from wafers cut along the height of Ingot C.

This shows that the addition of elemental calcium does not negativelyeffect the efficiency for solar cells made from wafers cut from the mainpart of the ingots but in effect tend to increase the efficiency.

The substantial increase in efficiency for solar cells made from waferscut at the lower end of Ingots B and D containing 40 ppmw elementalcalcium compared to the efficiency for solar cells made from wafers cutfrom ingots A and C, shows that the addition of elemental calcium to thesilicon before directional solidification substantially decreases thered zone in the silicon ingots, particularly in the lower end of theingots.

Example 2

Three directionally solidified multicrystalline silicon ingots E, F, andG of 16 kg each were produced in the same four chamber furnace asdescribed in Example 1. Ingot E was made from compensated siliconcontaining both boron and phosphorous produced by Elkem Solar AS,(ESS®), having a resistivity of between 1 and 1.3 ohm cm measured at thelower and of the Ingot. Ingot F was compensated silicon produced byElkem Solar, (ESS®), with addition of 100 ppmw elemental calciumaccording to the invention. Ingot G was polysilicon with addition of 100ppmw elemental calcium according to the invention and doped with boronto obtain a resistivity of between 1 and 1.3 ohm cm measured at thelower end of the ingot.

The height and cross-section of ingots E to G were the same as describedin Example 1. Further, 5 mm was cut away from the lower ends of ingots Eto G. Normal cuts were made from the sides of the ingots.

Wafers were cut along the height of ingots E to G and processed to solarcells using conventional processing methods and the efficiency of thesolar cells was measured, and the results are shown in FIGS. 5 and 6.

FIG. 5 shows the efficiency of solar cells made from wafers cut from thelower part of ingots E, F and G. As shown in FIG. 5 the efficiency ofsolar cells made from wafers from ingots F (compensated silicon to whichwas added 100 ppmw elemental calcium), and ingot G (polysilicon to whichwas added 100 ppmw elemental calcium), was much higher than for thesolar cells made from wafers from the lower part of ingot E, which didnot contain calcium. It can further be seen from FIG. 5 that solar cellsmade from wafers cut only about 5 mm from the bottom of ingot F and Ghad an efficiency of more than 16% to above 17% while solar cells madefrom wafers cut about 10 mm from the bottom of ingot E, showed anefficiency of below 15%.

Finally it can be seen from FIG. 5 that the solar cells made from thelower part of ingot F and G reached about 17% efficiency for wafers cutonly 5 mm from the lower end of the ingots while the same efficiency forsolar cells made from wafers from ingot E first reaches 17% efficiencywhen cut about 25 mm from the lower end of ingot A.

FIG. 6 shows the efficiency of solars cells made from wafers cut alongthe whole height of ingots E, F and G. It can be seen from FIG. 6 thatthe solar cells made from wafers from ingot F and G have a highefficiency along the total height of the ingots even towards the top ofthe ingots. For ingot E the efficiency starts to decrease at about 65 mmfrom the bottom of the ingot.

Example 2 shows that addition of 100 ppmw elemental calcium increasesthe efficiency of the lower part of the ingots substantially and evenmore than for the wafers of Example 1 with addition of 40 ppmw elementalcalcium.

Examples 1 and 2 show clearly that red zone is more or less eliminatedwith addition of elemental calcium to the silicon according to thepresent invention. The results also shows that thinner side cuts and topcuts can be done while maintaining a high efficiency of the solar cells.

A method has been invented according to the present invention to ensurea safe and convenient incorporation of calcium when added as asilicon-calcium masteralloy to a charge for producing directionallysolidified multicrystalline silicon ingot. Calcium is added as asilicon-calcium masteralloy with high Si content (80-99.5 weight %).

A method for adding calcium to a silicon melt through a masteralloy is amore secure and predictable method for adding calcium.

Example 3

Example 3 describes a method for producing a silicon-calcium masteralloyaccording to the present invention. The silicon-calcium masteralloy assuch and the method for producing said masteralloy must take place underneat conditions and has to exhibit a homogeneous distribution ofcalcium.

Silicon of high purity, like Elkem Solar Silicon®, is melted preferablyunder inert atmosphere. Calcium is added to molten silicon in an amountin the range 0.5-20 weight %. The molten charge is then homogenized bymixing thoroughly by stirring and thereafter solidified. Thesolidification must be performed under neatly controlled conditions toensure a rapid cooling of the molten charge. This can be done as a thincasting of low height by pouring the molten charge in cooled coppercrucibles. It is of importance that the calcium is homogenouslydistributed in the solidified cast masteralloy.

Several silicon-calcium masteralloys have been made by melting the puresilicon charge and subsequently adding calcium to the charge to obtainan alloy containing 0.5 to 20 weight % calcium. The molten masteralloyis homogenized for some minutes and then quenched rapidly. The level ofalloying elements is from 0.5-20%. The masteralloy can be produced indifferent shapes, for instance as cylindrical shapes of 20-50 mm ofdiameter and length varying from 10-100 mm. A typical size of the amountof added masteralloy is 100-300 g for a G5 furnace of 400-500 kg.

By inert atmosphere in this example it should be understood that inertatmosphere means at least one of the following gases: nitrogen, argon.

In the present example the masteralloy is as mentioned quenched rapidlywhich should be understood as a cooling rate of at least 10° C./minpreferably at least 50° C./min or more.

Example 4

This example relates to production of directionally solidified siliconingots where calcium is added to the silicon melt in the form of asilicon-calcium masteralloy. According to the invention adding calciumin the form of a silicon-calcium masteralloy, in which the percentage ofalloying element is in the range 0.5-20 weight %, has been tested in anindustrial G5 size ingot. G5 size ingot refers to generation 5 ingotfurnace which is common knowledge to a person skilled in the art. Bothreference ingots, polysilicon and compensated silicon produced by ElkemSolar AS (ESS®), and one ingot according to the present invention, wereproduced in the same furnace under the same conditions. In the ingotaccording to the invention compensated silicon produced by Elkem SolarAS (ESS®) was used with addition of 150 grams of a silicon-calciummasteralloy to the charge comprising the silicon.

The inclusion (particle) contents in the reference ingots and in theingot according to the invention as revealed by IR-images in FIG. 7 wasreduced in the ingot where silicon-calcium masteralloy had been added tothe silicon (the figure to the right compared to the ingot without themasteralloy as shown to the left in FIG. 7). FIG. 8 shows lifetime scansof one adjacent to centre brick from all four sides, a) for an ingotwith 100% virgin polysilicon made without addition of silicon-calciummasteralloy and average lifetime 4.0 μs, b) for an ingot with 100% ESS®with addition of silicon-calcium masteralloy and average lifetime 5.3 μsand c) for an ingot with 100% ESS® with addition of silicon-calciummasteralloy (bottom) and average lifetime 7.1 μs. Scale of the lifetimescan from 0.4 to 8 μs.

Wafers from the same brick position were processed to solar cells at ISCKonstanz in the same cell batch. FIG. 9 shows as mentioned above theefficiency of solar cells made from wafers cut from adjacent to centrebrick and corner brick from G5 ingot made with addition ofsilicon-calcium masteralloy compared to reference ingots (adjacent tocentre brick) of 100% virgin polysilicon and 100% ESS® made in the samefurnace. All wafers were processed at International Solar EnergyResearch Centre in Konstanz, Germany, (ISC). The results in FIG. 9 showan increase of 0.3% absolute in efficiency for the average of the wholebricks when compared to the polysilicon reference, and even morecompared to the reference of 100% ESS®.

Having described preferred embodiments of the invention it will beapparent to those skilled in the art that other embodimentsincorporating the concepts may be used. These and other examples of theinvention illustrated above are intended by way of example only and theactual scope of the invention is to be determined from the followingclaims.

The invention claimed is:
 1. A method for minimizing or removing the redzone in directional solidified multicrystalline silicon ingotscomprising adding calcium in its elemental form, or in the form of asilicon-calcium masteralloy comprising elemental calcium in an amount of0.5-20 weight %, the remaining being high purity silicon, to a siliconmelt in an amount chosen from one of the following ranges: 5-9.99 ppmw,10-500 ppmw, 500-550 ppmw prior to subjecting the silicon melt todirectional solidification in a crucible.
 2. The method according toclaim 1, wherein the calcium is added to the silicon melt in an amountchosen from one of the following ranges: 10-250, 20-250, 10-150, 20-150,10-100, ppmw.
 3. The method according to claim 1, wherein thesilicon-calcium masteralloy comprises elemental calcium in an amountchosen from one of the following ranges: 1-15 weight %, 5-15 weight %,the remaining being high purity silicon.
 4. The method according toclaim 1, wherein the silicon melt is chosen from one of the following: ahigh purity silicon melt, compensated silicon and polysilicon.
 5. Themethod according to claim 3, wherein the silicon-calcium masteralloy isadded to a charge comprising silicon for producing multicrystallinesilicon ingots.
 6. A directionally solidified multicrystalline siliconingot, wherein the ingot is obtained by the method according to claim 1.7. A method for preparing a silicon-calcium masteralloy for addition toa silicon melt when making directionally solidified multicrystallinesilicon ingot, wherein said silicon-calcium masteralloy compriseselemental calcium in an amount chosen from one of the following ranges:0.5-20 weight %, 1-15 weight %, 5-15 weight %, the remaining being highpurity silicon, the method comprising adding elemental calcium to amolten high purity silicon in an amount chosen from one of the followingranges 0.5-20 weight %, 1-15 weight %, 5-15 weight %, homogenizing aresulting alloy and solidifying the resulting alloy to provide thesilicon-calcium masteralloy.